Metal derivatives of orthocarbamyl-benzenethiol



Patented Aug. 30, 1949 METAL DERIVATIVES F on'rno- CARBAMYL-BENZENETHIOL Norbert Steiger, Nutley, and Oscar Keller, Clifton, N. J., assignors to Hoffmann-La Roche Inc., Nutley, N. J a corporation of New Jersey No Drawing. Application June 14, 1946, Serial N0; 676,862

This invention relates to new metal compounds of 0-carbamyl-benzenethiol and to their manufacture. f L

We have found that compounds of the formula:

C ONHi where Me is metal and v is its valence can be prepared by reacting a solution of carbamyl benze'nethiol (as solvents can -be used alcohol, acetone,- N NaOH, etc.) with solutions of metal salts in' a suitable solvent. For exampla'the zinc mercaptide can be made by dissolving carbamylbenzenethiol in N NaOI-I and adding an aqueous solution of zinc chloride in the presence of strongly diluted acetic acid. The bismuth compound can be made by the precipitation of a solution of carbamyl-benzenethiol in acetone with BiCla dissolved in acetone. 'The mercury compound is made by reacting the alcoholic solution of the mercaptan with an aqueous solution of mercuric acetate, etc. 1

The carbamyl-benzenethiol can be made according to GermanPatent 570,364.

The new metal compounds have a remarkable fungicidal and bactericidal activity. As they are very little soluble in water, they are either CONE:

whereinv is the valence of the metal Me.

Preparation of o-carbamyZ-benzenethiol -CN CN SOQNa. SO20] CONHi GONE,

SORH

11 Claims. (Cl. 260-429) 450 cc. monochlorbenzene and 150 grams PO15 were gradually'heated up to 90-95 C. in w e bath with 105 grams of the sodium salt of o-cyano-benzenesulfonic acid. The heating was continued for 3 hours, and the reaction mixture was allowed to cool overnight.

750 cc, cold water and then thoroughly triturated with 250 cc. 5% sodium acetate solution. After filtration, the precipitate was dissolved in 600 cc. N'2NaOH. The insoluble matter was filtered off and the clear filtrate was acidified to congo with HCl.

After cooling in the icebox overnight the white precipitate was filtered off, washed with cold water and dried invacuo'at room temperature.

The product was o-carbamyl-benzenethiol.

EXAMPLE 1 Zinc derivative of o-carbamyl-benzenethz'ol 15.5 grams of o-carbamyl-benzenethiol were dissolved in 1000 cc. H2O containing 110 cc. N NaOH. The turbid solution was filtered and the filtrate was slowly added to a solution of cc. 25% ZnC'lz and 100 cc. H20. 5 cc. 10% acetic acid were then added. The precipitated zinc compound was filtered ofi, washed with cold water and dried in vacuo at room temperature. The product was:

EXAMPLE 2 Mercury derivative of o-carbamyl-benzenethiol 3.1 grams of o-carbamyl-benzenethiol were dissolved in about 15 cc. hot alcohol. To this were added a. solution of 3.5 grams mercuric acetate in about 40 cc. water and 10 drops glacial acetic acid. The reaction mixture was well stirred and was cooled. The precipitate was filtered off,

washed with water and dried in vacuo. The product was:

CONH: HzNOC- sHg--s EXAMPLE 3 Silver derivative ofo-carbamyl-benzenethiol 3.1 grams of o-carbamyl-benzenethiol were dissolved in 40 cc. hot water containing excess NHiOH. To the solution were added. 3.7 grams AgNOa in excess NH4OH. The yellow precipitate was cooled, filtered ofi, washed with water and dried. The product was:

ONH:

SAg

EXAMPLE 4 Bismuth derivative of o-carbamyl-benzencthiol 6.2 gramsof o.-carbamyl-benzenethiol. were dissolved in 30 cc. hot alcohol. To this'was added a hot acidified alcoholic solution. of 4.7 grams BiCIs. The clear yellow solution was diluted with water. The yellow precipitate was filtered off, washed with water and dried. The product was:

Instead of alcohol, acetone can be employed.

EXAMPLE 5- Copper derivative of o-carbamyl-benzenethiol 3.]. grams o-carbamyl-benzenethiol were dissolved in 20. cc. hotalcohol'. The solution was added to 2.2 grams. cupric acetate in 100 cc. alcohol. The resulting. solution was diluted with water and. cooled. The gray precipitate was fil- Golal derivative of o-carbamyZ-Fbenzenethiol- 4.6 grams ofo-carbamyl-benzenethiol were dissolved in 15 cc. hot alcohol. To thiswere added- 3.55 grams gold chloride in about 10 cc. alcohol. The mixturewas well stirred and was cooled. The whiteprecipitate was filtered ofi', washed with water and dried. The product was:

C ONH:

4 We claim: 1. Compounds of the general formula:

CONH:

Metal wherein the metal is selected from the group consisting of silver, gold, zinc, copper, mercury and bismuth, and v is the valence of the metal.

2. Compound of claim 1 wherein the metal is zmc.

3. Compound of claim 1 wherein the metal is copper.

4. Compound of claim 1 wherein the metal is bismuth.

5. Process of making compounds of the general formula:

CONH:

Metal wherein the metal is selected from. the. group consisting of. si-Lver, gold, zinc, copper,. mercury and. bismuth, and v is the valence of the metal, which comprises reacting. carbamyl-benzenethiol with a metal salt selected from the group consisting of soluble salts of silver, gold, zinc, copper, mercury, and bismuth.

6. Process according tov claim 5 in which the reagents react in solution form.

'7. Process. according to claim 5 in which anaqueous solution of the salt is employed.

8. Process according to claim 5 employing zinc chloride.

9. Process according to claim 5 employing bismuth chloride.

10. Process according to claim 5 employing cupric acetate.

11. Process according to claim 5 employing ocarbamyl-benzenethiol' dissolved in ethanol.

NORBERT STEIGER. OSCAR- KELLER.

REFERENCES CITED The following references are of record in thefile of this patent:

UNITED STATES PATENTS OTHER REFERENCES Reissert et al., Chemical Abstracts, vol. 22, pages 4114-5 (1928).. 

